Iodopyrazolyl Carboxanilides

ABSTRACT

This invention relates to novel intermediates used in the preparation of iodopyrazolylcarboxanilides of the formula (I) 
     
       
         
         
             
             
         
       
     
     in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and Z are as defined in the disclosure, and to the preparation of such intermediates.

The present invention relates to novel iodopyrazolylcarboxanilides, to aplurality of processes for their preparation and to their use forcontrolling unwanted microorganisms.

It is already known that numerous carboxanilides have fungicidalproperties (cf., for example, WO 93/11117, EP-A 0 589 301, EP-A 0 545099, JP-A 2001-302605, JP-A 10-251240 and JP-A 8-176112). Thus,N-(2-cyclopentylphenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide,N-(2-cyclohexylphenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide,N-(2-cycloheptylphenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide,N-(2-cyclooctylphenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide andN-(2-bicyclo[2.2.1]hept-2-ylphenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamideare already known from WO 93/11117,N-(4′-chloro-1,1′-biphenyl-2-yl)-1,3-dimethyl-1H-pyrazole-4-carboxamideis already known from EP-A 0 589 301 andN-[2-(1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamideis already known from JP-A 10-251240. The activity of these compounds isgood; however, in some cases, for example at low application rates, itis unsatisfactory.

This invention now provides novel iodopyrazolylcarboxanilides of theformula (I)

in which

-   R¹, R², R³ and R⁴ independently of one another represent hydrogen,    fluorine, chlorine, methyl, isopropyl or methylthio,-   R⁵ represents hydrogen, C₁-C₈-alkyl, C₁-C₆-alkylsulfinyl,    C₁-C₆-alkylsulfonyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl;    C₁-C₆-haloalkyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl,    C₁-C₄-haloalkylsulfonyl, halo-C₁-C₄-alkoxy-C₁-C₄-alkyl,    C₃-C₈-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms, formyl-C₁-C₃-alkyl,    (C₁-C₃-alkyl)carbonyl-C₁-C₃-alkyl,    (C₁-C₃-alkoxy)carbonyl-C₁-C₃-alkyl;    (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-alkyl,    (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-alkyl having in each case 1 to 7    fluorine, chlorine and/or bromine atoms,    (C₁-C₃-alkyl)carbonyl-C₁-C₃-haloalkyl,    (C₁-C₃-alkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to 6    fluorine, chlorine and/or bromine atoms,    (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-haloalkyl,    (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to    13 fluorine, chlorine and/or bromine atoms; —COR⁷, —CONR⁸R⁹ or    —CH₂NR¹⁰R¹¹,-   R⁶ represents C₁-C₃-alkyl, C₁-C₂-alkoxy-C₁-C₂-alkyl, C₁-C₃-haloalkyl    having 1 to 7 fluorine, chlorine and/or bromine atoms,-   R⁷ represents hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy,    C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl; C₁-C₆-haloalkyl,    C₁-C₆-haloalkoxy, halo-C₁-C₄-alkoxy-C₁-C₄-alkyl,    C₃-C₈-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms, —COR¹²,-   R⁸ and R⁹ independently of one another represent hydrogen,    C₁-C₈-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl;    C₁-C₈-haloalkyl, halo-C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-halocycloalkyl    having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,-   R⁸ and R⁹ furthermore together with the nitrogen atom to which they    are attached form a saturated heterocycle which is optionally mono-    or polysubstituted by identical or different substituents from the    group consisting of halogen and C₁-C₄-alkyl and which has 5 to 8    ring atoms,    -   where the heterocycle may contain 1 or 2 further nonadjacent        heteroatoms from the group consisting of oxygen, sulfur and        NR¹³,-   R¹⁰ and R¹¹ independently of one another represent hydrogen,    C₁-C₈-alkyl, C₃-C₈-cycloalkyl; C₁-C₈-haloalkyl, C₃-C₈-halocycloalkyl    having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,-   R¹⁰ and R¹¹ furthermore together with the nitrogen atom to which    they are attached form a saturated heterocycle which is optionally    mono- or polysubstituted by identical or different substituents from    the group consisting of halogen and C₁-C₄-alkyl and which has 5 to 8    ring atoms, where the heterocycle may contain 1 or 2 further    nonadjacent heteroatoms from the group consisting of oxygen, sulfur    and NR¹³,-   R¹² represents hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy,    C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl; C₁-C₆-haloalkyl,    C₁-C₆-haloalkoxy, halo-C₁-C₄-alkoxy-C₁-C₄-alkyl,    C₃-C₈-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms,-   R¹³ represents hydrogen or C₁-C₆-alkyl,-   Z represents Z¹, Z² or Z³, where-   Z¹ represents phenyl which is optionally mono- to pentasubstituted    by identical or different substituents,-   Z² represents unsubstituted C₂-C₂₀-alkyl or represents C₁-C₂₀-alkyl    which is mono- or polysubstituted by identical or different    substituents from the group consisting of halogen and    C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may    optionally be mono- or polysubstituted by identical or different    substituents from the group consisting of halogen and C₁-C₄-alkyl,-   Z³ represents C₂-C₂₀-alkenyl or C₂-C₂₀-alkynyl, each of which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, hydroxyl and    C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may    optionally be mono- or polysubstituted by identical or different    substituents from the group consisting of halogen and C₁-C₄-alkyl,    or-   R¹, R² and R³ independently of one another represent hydrogen,    fluorine or chlorine and-   Z and R⁴ together with the carbon atoms to which they are attached    form an optionally substituted 5- or 6-membered carbocyclic or    heterocyclic ring.

Furthermore, it has been found that iodopyrazolylcarboxanilides of theformula (I) are obtained when

a) iodopyrazolylcarboxylic acid derivatives of the formula (II)

-   -   in which    -   R⁶ is as defined above and    -   X¹ represents chlorine or hydroxyl    -   are reacted with aniline derivatives of the formula (III)

-   -   in which R¹, R², R³, R⁴, R⁵ and Z are as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of a condensing agent, if appropriate in the        presence of an acid binder and if appropriate in the presence of        a diluent,        or

b) haloiodopyrazolylcarboxanilides of the formula (IV)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above and    -   X² represents chlorine, bromine, iodine or        trifluoromethylsulfonate    -   are reacted with boronic acid derivatives of the formula (V)

-   -   in which    -   Z¹ is as defined above and    -   A¹ and A² each represent hydrogen or together represent        tetramethylethylene,    -   in the presence of a catalyst, if appropriate in the presence of        an acid binder and if appropriate in the presence of a diluent,        or

c) iodopyrazolylcarboxamide boronic acid derivatives of the formula (VI)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above and    -   A³ and A⁴ each represent hydrogen or together represent        tetramethylethylene, are reacted with phenyl derivatives of the        formula (VII)

X³—Z¹  (VII)

-   -   in which    -   Z¹ is as defined above and    -   X³ represents chlorine, bromine, iodine or        trifluoromethylsulfonate, in the presence of a catalyst, if        appropriate in the presence of an acid binder and if appropriate        in the presence of a diluent,        or

d) haloiodopyrazolylcarboxanilides of the formula (IV)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above, and    -   X² represents chlorine, bromine, iodine or        trifluoromethylsulfonate,    -   are reacted with phenyl derivatives of the formula (VII)

X³—Z¹  (VII)

-   -   in which    -   Z¹ is as defined above and    -   X³ represents chlorine, bromine, iodine or        trifluoromethylsulfonate,    -   in the presence of a palladium or nickel catalyst and in the        presence of        4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane, if        appropriate in the presence of an acid binder and if appropriate        in the presence of a diluent,        or

e) iodopyrazolylcarboxanilides of the formula (Ia)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above and    -   X⁴ represents C₂-C₂₀-alkenyl or C₂-C₂₀-alkynyl, each of which is        optionally mono- or polysubstituted by identical or different        substituents from the group consisting of halogen and        C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may        optionally be substituted by halogen and/or C₁-C₄-alkyl,    -   are hydrogenated, if appropriate in the presence of a diluent        and if appropriate in the presence of a catalyst,        or

f) hydroxyalkyliodopyrazolylcarboxanilides of the formula (VIII)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above and    -   X⁵ represents C₂-C₂₀-hydroxyalkyl which is optionally        additionally mono- or polysubstituted by identical or different        substituents from the group consisting of halogen and        C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may        optionally be substituted by halogen and/or C₁-C₄-alkyl,    -   are dehydrated, if appropriate in the presence of a diluent and        if appropriate in the presence of an acid,        or

g) haloiodopyrazolylcarboxanilides of the formula (IV)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above, and

X² represents chlorine, bromine, iodine or trifluoromethylsulfonate,

-   -   are reacted with an alkine of the formula (IX)

-   -   in which    -   A⁵ represents C₂-C₁₈-alkyl which is optionally mono- or        polysubstituted by identical or different substituents from the        group consisting of halogen and C₃-C₆-cycloalkyl, where the        cycloalkyl moiety for its part may optionally be substituted by        halogen and/or C₁-C₄-alkyl,    -   or an alkene of the formula (X)

-   -   in which    -   A⁶, A⁷ and A⁸ independently of one another each represent        hydrogen or alkyl which is optionally mono- or polysubstituted        by identical or different substituents from the group consisting        of halogen and C₃-C₆-cycloalkyl, where the cycloalkyl moiety for        its part may optionally be substituted by halogen and/or        C₁-C₄-alkyl and the total number of carbon atoms of the        open-chain part of the molecule does not exceed the number 20,    -   if appropriate in the presence of a diluent, if appropriate in        the presence of an acid binder and    -   if appropriate in the presence of one or more catalysts,        or

h) ketones of the formula (XI)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above and    -   A⁹ represents hydrogen or C₁-C₁₈-alkyl which is optionally mono-        or polysubstituted by identical or different substituents from        the group consisting of halogen and C₃-C₆-cycloalkyl, where the        cycloalkyl moiety for its part may optionally be substituted by        halogen and/or C₁-C₄-alkyl,    -   are reacted with a phosphorus compound of the formula (XII)

A¹⁰-Px  (XII),

-   -   in which    -   A¹⁰ represents C₁-C₁₈-alkyl which is optionally mono- or        polysubstituted by identical or different substituents from the        group consisting of halogen and C₃-C₆-cycloalkyl, where the        cycloalkyl moiety for its part may optionally be substituted by        halogen and/or C₁-C₄-alkyl,    -   Px represents a grouping —P⁺(C₆H₅)₃Cl⁻, —P⁺(C₆H₅)₃Br⁻,        —P⁺(C₆H₅)₃I⁻, —P(═O)(OCH₃)₃ or —P(═O)(OC₂H₅)₃,    -   if appropriate in the presence of a diluent,        or

i) iodopyrazolylcarboxanilides of the formula (Ib)

-   -   in which    -   R¹, R², R³, R⁴, R⁶ and Z are as defined above,    -   are reacted with a halide of the formula (XIII)

—R⁵⁻¹—X⁶  (XIII)

-   -   in which    -   R⁵⁻¹ represents C₁-C₈-alkyl, C₁-C₆-alkylsulfinyl,        C₁-C₆-alkylsulfonyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl;        C₁-C₆-haloalkyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl,        C₁-C₄-haloalkylsulfonyl, halo-C₁-C₄-alkoxy-C₁-C₄-alkyl,        C₃-C₈-halocycloalkyl having in each case 1 to 9 fluorine,        chlorine and/or bromine atoms, formyl-C₁-C₃-alkyl,        (C₁-C₃-alkyl)carbonyl-C₁-C₃-alkyl,        (C₁-C₃-alkoxy)carbonyl-C₁-C₃-alkyl;        (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-alkyl,        (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-alkyl having in each case 1 to        7 fluorine, chlorine and/or bromine atoms,        (C₁-C₃-alkyl)carbonyl-C₁-C₃-haloalkyl,        (C₁-C₃-alkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to        6 fluorine, chlorine and/or bromine atoms,        (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-haloalkyl,        (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1        to 13 fluorine, chlorine and/or bromine atoms; —COR⁷, —CONR⁸R⁹        or —CH₂NR¹⁰R¹¹,    -   R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are as defined above and    -   X⁶ represents chlorine, bromine or iodine,    -   in the presence of a base and in the presence of a diluent.

Finally, it has been found that the novel iodopyrazolylcarboxanilides ofthe formula (I) have very good microbicidal properties and can be usedfor controlling unwanted microorganisms both in crop protection and inthe protection of materials.

Surprisingly, the iodopyrazolylcarboxanilides of the formula (I)according to the invention have considerably better fungicidal activitythan the constitutionally most similar active compounds of the prior arthaving the same direction of action.

If appropriate, the compounds according to the invention can be presentas mixtures of different possible isomeric forms, and in particular ofstereoisomers, such as, for example, E and Z, threo and erythro and alsooptical isomers, and, if appropriate, also of tautomers. What is claimedare both the E and the Z isomers, and the threo and erythro and also theoptical isomers, any mixtures of these isomers, and the possibletautomeric forms.

The formula (I) provides a general definition of theiodopyrazolylcarboxanilides according to the invention. Preferredradical definitions of the formulae mentioned above and below are givenbelow. These definitions apply both to the end products of the formula(I) and, correspondingly, to all intermediates.

-   R¹, R², R³ and R⁴ independently of one another preferably represent    hydrogen, fluorine, chlorine or methyl.-   R¹ particularly preferably represents hydrogen or fluorine.-   R¹ very particularly preferably represents hydrogen.-   R¹ also very particularly preferably represents fluorine.-   R² particularly preferably represents hydrogen.-   R³ particularly preferably represents hydrogen, fluorine, chlorine    or methylthio.-   R³ very particularly preferably represents hydrogen.-   R³ also very particularly preferably represents fluorine.-   R⁴ particularly preferably represents hydrogen, methyl or isopropyl.-   R⁴ very particularly preferably represents hydrogen.-   R⁴ also very particularly preferably represents methyl.-   R¹, R², R³ and R⁴ very particularly preferably all represent    hydrogen.-   R⁵ preferably represents hydrogen; C₁-C₆-alkyl, C₁-C₄-alkylsulfinyl,    C₁-C₄-alkylsulfonyl, C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆-cycloalkyl;    C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl,    C₁-C₄-haloalkylsulfonyl, halo-C₁-C₃-alkoxy-C₁-C₃-alkyl,    C₃-C₆-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms, formyl-C₁-C₃-alkyl,    (C₁-C₃-alkyl)carbonyl-C₁-C₃-alkyl,    (C₁-C₃-alkoxy)carbonyl-C₁-C₃-alkyl;    (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-alkyl,    (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-alkyl having in each case 1 to 7    fluorine, chlorine and/or bromine atoms,    (C₁-C₃-alkyl)carbonyl-C₁-C₃-haloalkyl,    (C₁-C₃-alkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to 6    fluorine, chlorine and/or bromine atoms,    (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-haloalkyl,    (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to    13 fluorine, chlorine and/or bromine atoms; —COR⁷, —CONR⁸R⁹ or    —CH₂NR¹⁰R¹¹.-   R⁵ particularly preferably represents hydrogen, methyl, ethyl, n- or    isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl,    methylsulfinyl, ethylsulfinyl, n- or isopropylsulfinyl, n-, iso-,    sec- or tert-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or    isopropylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl,    methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl,    cyclopentyl, cyclohexyl, trifluoromethyl, trichloromethyl,    trifluoroethyl, difluoromethylthio, difluorochloromethylthio,    trifluoromethylthio, trifluoromethylsulfinyl,    trifluoromethylsulfonyl, trifluoromethoxymethyl, —CH₂—CHO,    —CH₂CH₂—CHO, —CH₂—CO—CH₃, —CH₂—CO—CH₂CH₃, —CH₂—CO—CH(CH₃)₂,    —CH₂CH₂—CO—CH₃, —CH₂CH₂—CO—CH₂CH₃, —CH₂CH₂—CO—CH(CH₃)₂,    —CH₂—C(O)OCH₃, —CH₂—C(O)OCH₂CH₃, —CH₂—C(O)OCH(CH₃)₂,    —CH₂CH₂—C(O)OCH₃, —CH₂CH₂—C(O)OCH₂CH₃, —CH₂CH₂—C(O)OCH(CH₃)₂,    —CH₂—CO—CF₃, —CH₂—CO—CCl₃, —CH₂—CO—CH₂CF₃, —CH₂—CO—CH₂CCl₃,    —CH₂CH₂—CO—CH₂CF₃, —CH₂CH₂—CO—CH₂CCl₃, —CH₂—C(O)OCH₂CF₃,    —CH₂—C(O)OCF₂CF₃, —CH₂—C(O)OCH₂CCl₃, —CH₂—C(O)OCCl₂CCl₃,    —CH₂CH₂—C(O)OCH₂CF₃, —CH₂CH₂—C(O)OCF₂CF₃, —CH₂CH₂—C(O)OCH₂CCl₃,    —CH₂CH₂—C(O)O—CCl₂CCl₃; —COR⁷, —CONR⁸R⁹ or —CH₂NR¹⁰R¹¹.-   R⁵ very particularly preferably represents hydrogen; methyl,    methoxymethyl, —CH₂—CHO, —CH₂CH₂—CHO, —CH₂—CO—CH₃, —CH₂—CO—CH₂CH₃,    —CH₂—CO—CH(CH₃)₂ or —COR⁷.-   R⁶ preferably represents methyl, ethyl, isopropyl, monofluoromethyl,    difluoromethyl or trifluoromethyl.-   R⁶ particularly preferably represents methyl, ethyl or isopropyl.-   R⁶ very particularly preferably represents methyl.-   R⁷ preferably represents hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy,    C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆-cycloalkyl; C₁-C₄-haloalkyl,    C₁-C₄-haloalkoxy, halo-C₁-C₃-alkoxy-C₁-C₃-alkyl,    C₃-C₆-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms, —COR¹².-   R⁷ particularly preferably represents hydrogen, methyl, ethyl, n- or    isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy,    cyclopropyl; trifluoromethyl, trifluoromethoxy, —COR¹².-   R⁷ very particularly preferably represents hydrogen, —COCH₃, —CHO,    —COCH₂OCH₃, —COCO₂CH₃, —COCO₂CH₂CH₃.-   R⁸ and R⁹ independently of one another preferably represent    hydrogen, C₁-C₆-alkyl, C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆-cycloalkyl;    C₁-C₄-haloalkyl, halo-C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆-halocycloalkyl    having in each case 1 to 9 fluorine, chlorine and/or bromine atoms.-   R⁸ and R⁹ furthermore together with the nitrogen atom to which they    are attached preferably form a saturated heterocycle which is    optionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of halogen and C₁-C₄-alkyl    and which has 5 to 8 ring atoms, where the heterocycle may contain 1    or 2 further nonadjacent heteroatoms from the group consisting of    oxygen, sulfur and NR¹³.-   R⁸ and R⁹ independently of one another particularly preferably    represent hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec-    or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl,    ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl; trifluoromethyl,    trichloromethyl, trifluoroethyl, trifluoromethoxymethyl.-   R⁸ and R⁹ furthermore together with the nitrogen atom to which they    are attached particularly preferably form a saturated heterocycle    from the group consisting of morpholine, thiomorpholine and    piperazine, where the piperazine may be substituted at the second    nitrogen atom by R¹³, which heterocycle is optionally mono- to    tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine and methyl.-   R¹⁰ and R¹¹ independently of one another preferably represent    hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl; C₁-C₄-haloalkyl,    C₃-C₆-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms.-   R¹⁰ and R¹¹ furthermore together with the nitrogen atom to which    they are attached preferably form a saturated heterocycle which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen and C₁-C₄-alkyl    and which has 5 to 8 ring atoms, where the heterocycle may contain 1    or 2 further nonadjacent heteroatoms from the group consisting of    oxygen, sulfur and NR¹³.-   R¹⁰ and R¹¹ independently of one another particularly preferably    represent hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec-    or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl,    ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl; trifluoromethyl,    trichloromethyl, trifluoroethyl, trifluoromethoxymethyl.-   R¹⁰ and R¹¹ furthermore together with the nitrogen atom to which    they are attached particularly preferably form a saturated    heterocycle from the group consisting of morpholine, thiomorpholine    and piperazine, where the piperazine may be substituted at the    second nitrogen atom by R¹³, which heterocycle is optionally mono-    to tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine and methyl.-   R¹² preferably represents hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy,    C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆-cycloalkyl; C₁-C₄-haloalkyl,    C₁-C₄-haloalkoxy, halo-C₁-C₃-alkoxy-C₁-C₃-alkyl,    C₃-C₆-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms.-   R¹² particularly preferably represents hydrogen, methyl, ethyl, n-    or isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy,    cyclopropyl; trifluoromethyl, trifluoromethoxy.-   R¹³ preferably represents hydrogen or C₁-C₄-alkyl.-   R¹³ particularly preferably represents hydrogen, methyl, ethyl, n-    or isopropyl, n-, iso-, sec- or tert-butyl.-   Z preferably represents Z¹.-   Z¹ preferably represents phenyl which is optionally mono- to    pentasubstituted by identical or different substituents, where the    substituents are selected from the list W¹.-   Z¹ particularly preferably represents monosubstituted phenyl, where    the substituents are selected from the list W¹.-   Z¹ also particularly preferably represents phenyl which is    disubstituted by identical or different substituents, where the    substituents are selected from the list W¹.-   Z¹ also particularly preferably represents phenyl which is    trisubstituted by identical or different substituents, where the    substituents are selected from the list W¹.-   Z¹ very particularly preferably represents phenyl which is    monosubstituted in the 4-position, where the substituents are    selected from the list W¹.-   Z¹ very particularly preferably represents phenyl which is    disubstituted by identical or different substituents in the    3,4-position, where the substituents are selected from the list W¹.-   Z¹ very particularly preferably represents phenyl which is    disubstituted by identical or different substituents in the    2,4-position, where the substituents are selected from the list W¹.-   Z¹ very particularly preferably represents phenyl which is    disubstituted by identical or different substituents in the    3,5-position, where the substituents are selected from the list W¹.-   Z¹ very particularly preferably represents phenyl which is    trisubstituted by identical or different substituents in the    2,4,6-position, where the substituents are selected from the list    W¹.-   W¹ represents halogen, cyano, nitro, amino, hydroxyl, formyl,    carboxyl, carbamoyl, thiocarbamoyl;    -   in each case straight-chain or branched alkyl, hydroxyalkyl,        oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl,        alkylthio, alkylsulfinyl or alkylsulfonyl having in each case 1        to 8 carbon atoms;    -   in each case straight-chain or branched alkenyl or alkenyloxy        having in each case 2 to 6 carbon atoms;    -   in each case straight-chain or branched haloalkyl, haloalkoxy,        haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl having in        each case 1 to 6 carbon atoms and 1 to 13 identical or different        halogen atoms;    -   in each case straight-chain or branched haloalkenyl or        haloalkenyloxy having in each case 2 to 6 carbon atoms and 1 to        11 identical or different halogen atoms;    -   in each case straight-chain or branched alkylamino,        dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,        alkylaminocarbonyl, dialkylaminocarbonyl,        arylalkylaminocarbonyl, dialkylaminocarbonyloxy having 1 to 6        carbon atoms in the respective hydrocarbon chains,        alkenylcarbonyl or alkynylcarbonyl having 2 to 6 carbon atoms in        the respective hydrocarbon chains;    -   cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon        atoms;    -   in each case doubly attached alkylene having 3 or 4 carbon        atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene        having 1 or 2 carbon atoms, each of which radicals is optionally        mono- to tetrasubstituted by identical or different substituents        from the group consisting of fluorine, chlorine, oxo, methyl,        trifluoromethyl and ethyl;    -   or a grouping —C(Q¹)=N-Q², in which    -   Q¹ represents hydrogen, hydroxyl or alkyl having 1 to 4 carbon        atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical        or different halogen atoms or cycloalkyl having 1 to 6 carbon        atoms and    -   Q² represents hydroxyl, amino, methylamino, phenyl, benzyl or        represents in each case optionally halo, cyano-, hydroxyl-,        alkoxy-, alkylthio-, alkylamino-, dialkylamino- or        phenyl-substituted alkyl or alkoxy having 1 to 4 carbon atoms,        or represents alkenyloxy or alkynyloxy having in each case 2 to        4 carbon atoms,    -   and also phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl,        cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy,        phenylalkylthio or heterocyclylalkyl having in each case 1 to 3        carbon atoms in the respective alkyl moieties, each of which        radicals is optionally mono- to trisubstituted in the cyclic        part by halogen and/or straight-chain or branched alkyl or        alkoxy having 1 to 4 carbon atoms.-   W¹ preferably represents fluorine, chlorine, bromine, methyl, ethyl,    n- or i-propyl, n-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,    trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,    difluorochloromethoxy, trifluoroethoxy, in each case doubly attached    difluoromethylenedioxy or tetrafluoroethylenedioxy, or a grouping    —C(Q¹)=N-Q², where    -   Q¹ represents hydrogen, methyl, ethyl, trifluoromethyl or        cyclopropyl and    -   Q² represents hydroxyl, methoxy, ethoxy, propoxy or isopropoxy.-   Z also preferably represents Z².-   Z² preferably represents unsubstituted C₂-C₂₀-alkyl or represents    C₁-C₂₀-alkyl which is mono- or polysubstituted by identical or    different substituents from the group consisting of fluorine,    chlorine, bromine, iodine and C₃-C₆-cycloalkyl, where the cycloalkyl    moiety for its part may optionally be mono- to tetrasubstituted by    identical or different substituents from the group consisting of    fluorine, chlorine, bromine, iodine, C₁-C₄-alkyl and    C₁-C₄-haloalkyl.-   Z² particularly preferably represents unsubstituted C₂-C₂₀-alkyl.-   Z² also particularly preferably represents C₁-C₂₀-alkyl which is    substituted by chlorine, cyclopropyl, dichlorocyclopropyl,    cyclobutyl, cyclopentyl or cyclohexyl.-   Z also preferably represents Z³.-   Z³ preferably represents C₂-C₂₀-alkenyl or C₂-C₂₀-alkynyl, each of    which is optionally mono- or polysubstituted by identical or    different substituents from the group consisting of fluorine,    chlorine, bromine, iodine, hydroxyl and C₃-C₆-cycloalkyl, where the    cycloalkyl moiety for its part may optionally be mono- to    tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine, iodine, C₁-C₄-alkyl    and C₁-C₄-haloalkyl.-   Z³ particularly preferably represents C₂-C₂₀-alkenyl or    C₂-C₂₀-alkynyl.-   Z³ very particularly preferably represents ethenyl, propenyl,    butenyl, pentenyl, hexenyl, heptenyl, propynyl, butynyl, pentynyl,    hexynyl or heptynyl.-   Z and R⁴ also preferably together with the carbon atoms to which    they are attached represent a 5- or 6-membered carbocyclic or    heterocyclic ring which is optionally mono- to tetrasubstituted by    identical or different substituents.-   Z and R⁴ also particularly preferably together with the carbon atoms    to which they are attached represent a 5- or 6-membered carbocyclic    ring which is optionally mono-, di- or trisubstituted by methyl.-   Z and R⁴ also very particularly preferably together with the carbon    atoms to which they are attached represent *—CH(CH₃)—CH₂—C(CH₃)₂—,    —(CH₂)₃—, —CH(CH₃)—CH₂—CH(CH₃)—, where the bond marked * is attached    to Z.

Preference is furthermore given to compounds of the formula (Ic)

in which

R¹, R², R³, R⁴, R⁶ and Z¹ are as defined above.

Particular preference is given to compounds of the formula (Ic) in whichR⁶ represents methyl.

Preference is furthermore given to compounds of the formula (Id)

in which

R¹, R², R³, R⁴, R⁶ and Z² are as defined above.

Particular preference is given to compounds of the formula (Id) in whichR⁶ is methyl.

Preference is furthermore given to compounds of the formula (Ie)

in which

R¹, R², R³, R⁴, R⁶ and Z³ are as defined above.

Particular preference is given to compounds of the formula (Ie) in whichR⁶ is methyl.

Preference is furthermore given to compounds of the formula (Ib)

in which

R¹, R², R³, R⁴, R⁶ and Z are as defined above.

Particular preference is given to compounds of the formula (Ib) in whichR⁶ is methyl.

Preference is furthermore given to compounds of the formula (If)

in which

R¹, R², R³, R⁴, R⁵⁻¹, R⁶ and Z are as defined above.

-   R⁵⁻¹ preferably represents C₁-C₆-alkyl, C₁-C₄-alkylsulfinyl,    C₁-C₄-alkylsulfonyl, C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆-cycloalkyl;    C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl,    C₁-C₄-haloalkylsulfonyl, halo-C₁-C₃-alkoxy-C₁-C₃-alkyl,    C₃-C₆-halocycloalkyl having in each case 1 to 9 fluorine, chlorine    and/or bromine atoms, formyl-C₁-C₃-alkyl,    (C₁-C₃-alkyl)carbonyl-C₁-C₃-alkyl,    (C₁-C₃-alkoxy)carbonyl-C₁-C₃-alkyl;    (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-alkyl,    (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-alkyl having in each case 1 to 7    fluorine, chlorine and/or bromine atoms,    (C₁-C₃-alkyl)carbonyl-C₁-C₃-haloalkyl,    (C₁-C₃-alkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to 6    fluorine, chlorine and/or bromine atoms,    (C₁-C₃-haloalkyl)carbonyl-C₁-C₃-haloalkyl,    (C₁-C₃-haloalkoxy)carbonyl-C₁-C₃-haloalkyl having in each case 1 to    13 fluorine, chlorine and/or bromine atoms; —COR⁷, —CONR⁸R⁹ or    —CH₂NR¹⁰R¹¹.-   R⁵⁻¹ particularly preferably represents methyl, ethyl, n- or    isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl,    methylsulfinyl, ethylsulfinyl, n- or isopropylsulfinyl, n-, iso-,    sec- or tert-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or    isopropylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl,    methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl,    cyclopentyl, cyclohexyl, trifluoromethyl, trichloromethyl,    trifluoroethyl, difluoromethylthio, difluorochloromethylthio,    trifluoromethylthio, trifluoromethylsulfinyl,    trifluoromethyl-sulfonyl, trifluoromethoxymethyl, —CH₂—CHO,    —CH₂CH₂—CHO, —CH₂—CO—CH₃, —CH₂—CO—CH₂CH₃, —CH₂—CO—CH(CH₃)₂,    —CH₂CH₂—CO—CH₃, —CH₂CH₂—CO—CH₂CH₃, —CH₂CH₂—CO—CH(CH₃)₂,    —CH₂—C(O)OCH₃, —CH₂—C(O)OCH₂CH₃, —CH₂—C(O)OCH(CH₃)₂,    —CH₂CH₂—C(O)OCH₃, —CH₂CH₂—C(O)OCH₂CH₃, —CH₂CH₂—C(O)OCH(CH₃)₂,    —CH₂—CO—CF₃, —CH₂—CO—CCl₃, —CH₂—CO—CH₂CF₃, —CH₂—CO—CH₂CCl₃,    —CH₂CH₂—CO—CH₂CF₃, —CH₂CH₂—CO—CH₂CCl₃, —CH₂—C(O)OCH₂CF₃,    —CH₂—C(O)OCF₂CF₃, —CH₂—C(O)OCH₂CCl₃, —CH₂—C(O)OCCl₂CCl₃,    —CH₂CH₂—C(O)OCH₂CF₃, —CH₂CH₂—C(O)OCF₂CF₃, —CH₂CH₂—C(O)OCH₂CCl₃,    —CH₂CH₂—C(O)O—CCl₂CCl₃; —COR⁷, —CONR⁸R⁹ or —CH₂NR¹⁰R¹¹.-   R⁵⁻¹ very particularly preferably represents methyl, methoxymethyl,    —CH₂—CHO, —CH₂CH₂—CHO, —CH₂—CO—CH₃, —CH₂—CO—CH₂CH₃, —CH₂—CO—CH(CH₃)₂    or —COR⁷.

Particular preference is given to compounds of the formula (If) in whichR⁶ represents methyl.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl,can in each case be straight-chain or branched as far as this ispossible, including in combination with heteroatoms, such as, forexample, in alkoxy.

The definition C₁-C₂₀-alkyl embraces the widest range defined here foran alkyl radical. Specifically, this definition includes the meaningsmethyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl, and in eachcase all isomeric pentyls, hexyls, heptyls, octyls, nonyls, decyls,undecyls, dodecyls, tridecyls, tetradecyls, pentadecyls, hexadecyls,heptadecyls, octadecyls, nonadecyls and eicosyls. Among these, themeanings methyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl,n-pentyl, 1-methylbutyl, 2-methyl-butyl, 3-methylbutyl,1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, 1-methylpentyl,4-methyl-pentyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl,1,2,2-trimethylpropyl, n-heptyl, 1-methylhexyl, 5-methylhexyl,1,4-dimethylpentyl, 4,4-dimethylpentyl, 1,3,3-trimethylbutyl,1,2,3-trimethylbutyl are preferred.

The definition C₂-C₂₀-alkenyl embraces the widest range defined here foran alkenyl radical. Specifically, this definition includes the meaningsethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, and in eachcase all isomeric pentenyls, hexenyls, heptenyls, octenyls, nonenyls,decenyls, undecenyls, dodecenyls, tridecenyls, tetradecenyls,pentadecenyls, hexadecenyls, heptadecenyls, octadecenyls, nonadecenylsand eicosenyls. Among these, preference is given to the meaningsethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 1,2-dimethyl-1-propenyl, 1-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 1,3-dimethyl-1-butenyl, 1-methyl-1-hexenyl,1,3,3-trimethyl-1-butenyl.

The definition C₂-C₂₀-alkynyl embraces the widest range defined here foran alkynyl radical. Specifically, this definition includes the meaningsethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, and in each case all isomeric pentynyls, hexynyls,heptynyls, octynyls, nonynyls, decynyls, undecynyls, dodecynyls,tridecynyls, tetradecynyls, pentadecynyls, hexadecynyls, heptadecynyls,octadecynyls, nonadecynyls and eicosynyls. Among these, preference isgiven to the meanings ethynyl, 1-propynyl, 1-butynyl, 3-butynyl,1-methyl-2-propynyl, 1-pentynyl, 4-pentynyl, 1-hexynyl, 5-hexynyl,3,3-dimethyl-1-butynyl, 4,4-dimethyl-1-pentynyl,4,4-dimethyl-2-pentynyl, 1,4-dimethyl-2-pentynyl.

Optionally substituted radicals may be mono- or polysubstituted, wherein the case of polysubstitution the substituents can be identical ordifferent.

Halogen-substituted radicals, such as, for example, haloalkyl, are mono-or polyhalogenated. In the case of polyhalogenation, the halogen atomscan be identical or different. Here, halogen denotes fluorine, chlorine,bromine and iodine, in particular fluorine, chlorine and bromine

The general or preferred radical definitions or illustrations givenabove can be combined between the respective ranges and preferred rangesas desired. The definitions apply both to the end products and,correspondingly, to the precursors and intermediates.

Explanations of the Processes and Intermediates:

Process (a)

Using 3-iodo-1-methyl-1H-pyrazole-4-carboxylic acid and3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-amine as starting materials, thecourse of the process (a) according to the invention can be illustratedby the formula scheme below.

Formula (II) provides a general definition of theiodopyrazolylcarboxylic acid derivatives required as starting materialsfor carrying out the process (a) according to the invention. In thisformula (II), X′ preferably represents chlorine or hydroxyl.

Some of the iodopyrazolylcarboxylic acid derivatives of the formula (II)are known. They are obtained when

j) 3-aminopyrazole-4-carboxylic esters of the formula (XIV)

-   -   in which    -   Alk represents C₁-C₄-alkyl and    -   R⁶ is as defined above,    -   are reacted in a first step with an iodonating agent (for        example methylene iodide) in the presence of isoamyl nitrite    -   and the resulting 3-iodopyrazole-4-carboxylic esters of the        formula (XV)

-   -   in which Alk and R⁶ are as defined above,    -   are in a second step hydrolyzed to the acid using a base (for        example NaOH or KOH) in the presence of a diluent (for example        ethanol)    -   and this acid [compounds of the formula (II) in which X¹        represents hydroxyl] is, if appropriate, reacted in a third step        with a chlorinating agent (for example thionyl chloride/oxalyl        chloride) in the presence of a diluent (for example toluene or        methylene chloride) to give the corresponding acid chloride        [compounds of the formula (II) in which X¹ represents chlorine].

In the compounds of the formulae (XIV) and (XV), R⁶ preferably,particularly preferably and very particularly preferably has thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred and veryparticularly preferred, respectively, for these radicals.

Some of the compounds of the formulae (XIV) and (XV) are known (cf. WO93/11117, JP 2002-128763). 3-Aminopyrazole-4-carboxylic esters of theformula (XIV) are furthermore obtained when

k) benzylidenehydrazine derivatives of the formula (XVI)

-   -   in which R⁶ and Alk are as defined above    -   are cyclized in the presence of an acid (for example HCl) and in        the presence of a diluent (for example ethanol).

In the compounds of the formula (XVI), R⁶ preferably, particularlypreferably and very particularly preferably has those meanings whichhave already been mentioned in connection with the description of thecompounds of the formula (I) according to the invention as beingpreferred, particularly preferred and very particularly preferred,respectively, for these radicals.

The compounds of the formula (XVI) are novel. They are obtained when

l) benzylidenehydrazines of the formula (XVII)

-   -   in which R⁶ is as defined above    -   are reacted with cyanoacetic esters of the formula (XVIII)

-   -   in which Alk is as defined above    -   in the presence of a diluent (for example toluene) (cf. J. Org.        Chem. 1983, 48, 4116-4119).

The benzylidenehydrazines of the formula (XVII) and the cyanoaceticesters of the formula (XVIII) are known and/or can be prepared by knownmethods.

The formula (III) provides a general definition of the anilinederivatives furthermore required as starting materials for carrying outthe process (a) according to the invention. In this formula R¹, R², R³,R⁴, R⁵ and Z preferably, particularly preferably and very particularlypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferredand very particularly preferred, respectively, for these radicals.

Most of the starting materials of the formula (III) are known, and/orthey can be prepared by known processes (cf., for example, Bull. KoreanChem. Soc. 2000, 21, 165-166; Chem. Pharm. Bull. 1992, 40, 240-244;Heterocycles 1989, 29, 1013-1016; J. Med. Chem. 1996, 39, 892-903;Synthesis 1995, 713-16; Synth. Commun. 1994, 24, 267-272; Synthesis1994, 142-144; DE-A 27 27 416; DE-A 102 190 35; JP-A 9-132567; EP-A 0824 099; WO 93/11117; EP-A 0 545 099; EP-A 0 589 301; EP-A 0 589 313 andWO 02/38542).

It is also possible to prepare initially aniline derivatives of theformula (III) in which R⁵ is hydrogen and then to derivatize thecompounds obtained using customary methods (for example analogously tothe process (i) according to the invention).

Process (b)

Using N-(2-bromophenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide and4-chloro-3-fluorophenylboronic acid as starting materials and acatalyst, the course of the process (b) according to the invention canbe illustrated by the formula scheme below.

The formula (IV) provides a general definition of thehaloiodopyrazolylcarboxanilides required as starting materials forcarrying out the process (b) according to the invention. In this formula(IV), R¹, R², R³, R⁴, R⁵ and R⁶ preferably, particularly preferably andvery particularly preferably have those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred and very particularly preferred, respectively, for theseradicals. X² is bromine or iodine.

The haloiodopyrazolylcarboxanilides of the formula (IV) have hithertonot been disclosed. As novel chemical compounds, they also form part ofthe subject-matter of the present application. They are obtained when

m) iodopyrazolylcarboxylic acid derivatives of the formula (II)

-   -   in which    -   X¹ is chlorine or hydroxyl,    -   R⁶ is as defined above    -   are reacted with haloanilines of the formula (XIX)

-   -   in which R¹, R², R³, R⁴, R⁵ and X² are as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of a condensing agent, if appropriate in the        presence of an acid binder and if appropriate in the presence of        a diluent.

Process (m)

Using 3-iodo-1-methyl-1H-pyrazole-4-carbonyl chloride and 2-bromoanilineas starting materials, the course of the process (m) according to theinvention can be illustrated by the formula scheme below.

The iodopyrazolylcarboxylic acid derivatives of the formula (II)required as starting materials for carrying out the process (m)according to the invention have already been described further above, inconnection with the process (a) according to the invention.

The formula (XIX) provides a general definition of the haloanilinesfurthermore required as starting materials for carrying out the process(m) according to the invention. In this formula (XIX), R¹, R², R³, R⁴,R⁵ and X² preferably, particularly preferably and very particularlypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention or the intermediates of the formula (III) asbeing preferred, particularly preferred and very particularly preferred,respectively, for these radicals.

The haloanilines of the formula (XIX) are known chemicals for synthesisor can be obtained by known processes. If R⁵ does not representhydrogen, the radical R⁵ can be introduced at the stage of the compoundsof the formula (XIX) using customary derivatization methods. It is alsopossible to prepare initially compounds of the formula (IV) in which R⁵is hydrogen and then to derivatize the products obtained using customarymethods (cf. the process (i) according to the invention).

The formula (V) provides a general definition of the boronic acidderivatives furthermore required as starting materials for carrying outthe process (b) according to the invention. In this formula (V), Z¹preferably, particularly preferably and very particularly preferably hasthose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred and veryparticularly preferred, respectively, for Z¹. A¹ and A² each representhydrogen or together represent tetramethylethylene.

The boronic acid derivatives of the formula (V) are known and/or can beprepared by known processes (cf., for example, WO 01/90084 and U.S. Pat.No. 5,633,218).

Process (c)

Using 2-{[(3-iodo-1-methyl-1H-pyrazole-4-yl)carbonyl]amino}phenylboronicacid and 1-bromo-4-chloro-3-fluorobenzene as starting materials and acatalyst, the course of the process (c) according to the invention canbe illustrated by the formula scheme below.

The formula (VI) provides a general definition of theiodopyrazolylcarboxamide boronic acid derivatives required as startingmaterials for carrying out the process (c) according to the invention.In this formula (VI), R¹, R², R³, R⁴, R⁵ and R⁶ preferably, particularlypreferably and very particularly preferably have those meanings whichhave already been mentioned in connection with the description of thecompounds of the formula (I) according to the invention as beingpreferred, particularly preferred and very particularly preferred,respectively, for these radicals. A³ and A⁴ each represent hydrogen ortogether represent tetramethylethylene.

The iodopyrazolylcarboxamideboronic acid derivatives of the formula (VI)have hitherto not been disclosed. They are novel chemical compounds andalso form part of the subject-matter of the present application. Theyare obtained when

n) iodopyrazolylcarboxylic acid derivatives of the formula (II)

-   -   in which    -   X¹ represents chlorine or hydroxyl,    -   R⁶ is as defined above    -   are reacted with anilineboronic acid derivatives of the formula        (XX)

-   -   in which    -   R¹, R², R³, R⁴, R⁵, A³ and A⁴ are as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of a condensing agent, if appropriate in the        presence of an acid binder and if appropriate in the presence of        a diluent.

Process (n)

Using 3-iodo-1-methyl-1H-pyrazole-4-carbonyl chloride and2-aminophenylboronic acid as starting materials, the course of theprocess (n) according to the invention can be illustrated by the formulascheme below.

The iodopyrazolylcarboxylic acid derivatives of the formula (II)required as starting materials for carrying out the process (n)according to the invention have already been described further above, inconnection with the process (a) according to the invention.

The formula (XX) provides a general definition of the anilineboronicacid derivatives furthermore required as starting materials for carryingout the process (n) according to the invention. In this formula (XX),R¹, R², R³, R⁴, R⁵ and R⁶ preferably, particularly preferably and veryparticularly preferably have those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred and very particularly preferred, respectively, for theseradicals. A³ and A⁴ each represent hydrogen or together representtetramethylethylene.

The anilineboronic acid derivatives of the formula (XX) are knownchemicals for synthesis or can be obtained by known processes. If R⁵does not represent hydrogen, the radical R⁵ can be introduced at thestage of the compounds of the formula (XX) using customaryderivatization methods. It is also possible to prepare initiallycompounds of the formula (VI) in which R⁵ represents hydrogen and thento derivatize the products obtained using customary methods (cf. theprocess (i) according to the invention).

The formula (VII) provides a general definition of the phenylderivatives furthermore required as starting materials for carrying outthe process (c) according to the invention. In this formula (VII), Z¹preferably, particularly preferably and very particularly preferably hasthose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred and veryparticularly preferred, respectively, for Z¹. X³ represents chlorine,bromine, iodine or trifluoromethylsulfonate.

The phenyl derivatives of the formula (VII) are known chemicals forsynthesis.

Process (d)

Using N-(2-bromophenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide and1-bromo-4-chloro-3-fluorobenzene as starting materials and a catalystand 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane, thecourse of the process (d) according to the invention can be illustratedby the formula scheme below.

The haloiodopyrazolylcarboxanilides of the formula (IV) and the phenylderivatives of the formula (VII) required as starting materials forcarrying out the process (d) according to the invention have alreadybeen described further above, in connection with the processes (b) and(c) according to the invention.

4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane, furthermorerequired for carrying out the process (d) according to the invention, isa commercially available chemical for synthesis.

Process (e)

If, for example,N-{2-[1,3-dimethyl-1-butenyl]phenyl}-3-iodo-1-methyl-1H-pyrazole-4-carboxamideis hydrogenated, the course of the process (e) according to theinvention can be illustrated by the formula scheme below.

Formula (Ia) provides a general definition of theiodopyrazolylcarboxanilides required as starting materials for carryingout the process (e) according to the invention. In this formula (Ia),R¹, R², R³, R⁴, R⁵ and R⁶ preferably, particularly preferably and veryparticularly preferably have those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred and very particularly preferred, respectively, for theseradicals.

The compounds of the formula (Ia) are compounds according to theinvention and can be prepared by processes (a), (f), (g) or (h).

Process (f)

If, for example,N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-3-iodo-1-methyl-1H-pyrazole-4-carboxamideis dehydrated, the course of the process (f) according to the inventioncan be illustrated by the formula scheme below.

The formula (VIII) provides a general definition of thehydroxyalkyliodopyrazolylcarboxanilides required as starting materialsfor carrying out the process (f) according to the invention. In thisformula (VIII), R¹, R², R³, R⁴, R⁵ and R⁶ preferably, particularlypreferably and very particularly preferably have those meanings whichhave already been mentioned in connection with the description of thecompounds of the formula (I) according to the invention as beingpreferred, particularly preferred and very particularly preferred,respectively, for these radicals.

-   X⁵ preferably represents C₂-C₁₂-hydroxyalkyl which is optionally    additionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of chlorine, fluorine,    bromine and/or C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its    part may optionally be substituted by halogen and/or C₁-C₄-alkyl.-   X⁵ particularly preferably represents in each case straight-chain or    branched hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl,    hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl or    hydroxydecyl, each of which may be attached in any position and each    of which is optionally mono- to tetrasubstituted by identical or    different substituents from the group consisting of fluorine,    cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and    cyclohexyl.

The compounds of the formula (VIII) have hitherto not been disclosedand, as novel compounds, also form part of the subject-matter of thepresent application.

It has also been found that the hydroxyalkyliodopyrazolylcarboxanilidesof the formula (VIII) have very good microbicidal properties and can beused for controlling unwanted microorganisms both in crop protection andin the protection of materials.

The hydroxyalkyliodopyrazolylcarboxanilides of the formula (VIII) areobtained when

o) iodopyrazolylcarboxylic acid derivatives of the formula (II)

-   -   in which    -   X¹ represents chlorine or hydroxyl,    -   R⁶ is as defined above,    -   are reacted with hydroxyalkylaniline derivatives of the formula        (XXI)

-   -   in which    -   R¹, R², R³, R⁴, R⁵ and X⁵ are as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of a condensing agent, if appropriate in the        presence of an acid binder and if appropriate in the presence of        a diluent.

Process (O)

Using, for example, 3-iodo-1-methyl-1H-pyrazole-4-carbonyl chloridecarbonyl chloride and 2-(2-aminophenyl)-2-pentanol as startingmaterials, the course of the process (O) according to the invention canbe illustrated by the formula scheme below:

The iodopyrazolylcarboxylic acid derivatives of the formula (II)required as starting materials for carrying out the process (O)according to the invention have already been described further above, inconnection with the process (a) according to the invention.

The formula (XXI) provides a general definition of thehydroxyalkylaniline derivatives furthermore required as startingmaterials for carrying out the process (O) according to the invention.In this formula (XXI), R¹, R², R³, R⁴, R⁵ and X⁵ preferably,particularly preferably and very particularly preferably have thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formulae (I) and (VIII) according tothe invention as being preferred, particularly preferred and veryparticularly preferred, respectively, for these radicals.

The hydroxyalkylaniline derivatives of the formula (XXI) are knownand/or can be obtained by known methods (cf., for example, U.S. Pat. No.3,917,592 or EP-A 0 824 099). If R⁵ does not represent hydrogen, theradical R⁵ can be introduced at the stage of the compounds of theformula (XXI) using customary derivatization methods. It is alsopossible to prepare initially compounds of the formula (VIII) in whichR⁵ represents hydrogen and then to derivatize the products obtainedusing customary methods (cf. the process (i) according to theinvention).

Process (g)

Using, for example,N-(2-bromophenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide and 1-hexyneas starting materials and a catalyst, the course of the process (g)according to the invention can be illustrated by the formula schemebelow.

The haloiodopyrazolylcarboxanilides of the formula (IV) required asstarting materials for carrying out the process (g) according to theinvention have already been described further above, in connection withthe process (c) according to the invention.

The formula (IX) provides a general definition of the alkynesfurthermore required as starting materials for carrying out the process(g) according to the invention.

-   A⁵ preferably represents C₂-C₁₀-alkyl which is optionally mono- to    tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine and    C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may    optionally be substituted by halogen and/or C₁-C₄-alkyl.-   A⁵ particularly preferably represents in each case straight-chain or    branched ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, each    of which may be attached in any position and each of which is mono-    to tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, cyclopropyl,    difluorocyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The alkynes of the formula (IX) are known chemicals for synthesis.

The formula (X) provides a general definition of the alkenes furthermorealternatively required as starting materials for carrying out theprocess (g) according to the invention.

-   A⁶, A⁷ and A⁸ independently of one another preferably each represent    hydrogen or alkyl which is optionally mono- to tetrasubstituted by    identical or different substituents from the group consisting of    fluorine, chlorine, bromine and C₃-C₆-cycloalkyl, where the    cycloalkyl moiety for its part may optionally be substituted by    halogen and/or C₁-C₄-alkyl and where the total number of carbon    atoms of the open-chain part of the molecule does not exceed the    number 12.-   A⁶, A⁷ and A⁸ independently of one another particularly preferably    each represent hydrogen or in each case straight-chain or branched    ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, each of which    may be attached in any position and each of which is optionally    mono- to tetrasubstituted by identical or different substituents    from the group consisting of fluorine, cyclopropyl,    difluorocyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, where    the total number of carbon atoms of the open-chain part of the    molecule does not exceed the number 12.

The alkenes of the formula (X) are known chemicals for synthesis.

Process (h)

Using N-(2-acetylphenyl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide andbutyl(triphenyl)phosphonium iodide as starting materials, the course ofthe process (h) according to the invention can be illustrated by theformula scheme below:

The formula (XI) provides a general definition of the ketones requiredas starting materials for carrying out the process (h) according to theinvention. In this formula, R¹, R², R³, R⁴, R⁵ and R⁶ preferably,particularly preferably and very particularly preferably have thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred and veryparticularly preferred, respectively, for these radicals.

-   A⁹ preferably represents C₂-C₁₀-alkyl which is optionally mono- to    tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine and    C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may    optionally be substituted by halogen and/or C₁-C₄-alkyl.-   A⁹ particularly preferably represents in each case straight-chain or    branched, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, each    of which may be attached in any position and each of which is    optionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of fluorine, cyclopropyl,    difluorocyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The ketones of the formula (XI) have hitherto not been disclosed. Asnovel chemical compounds, they also form part of the subject-matter ofthe present application. They are obtained when

p) iodopyrazolylcarboxylic acid derivatives of the formula (II)

-   -   in which    -   X¹ represents chlorine or hydroxyl,    -   R⁶ is as defined above,    -   are reacted with ketoanilines of the formula (XXII)

-   -   in which R¹, R², R³, R⁴, R⁵ and A⁹ are as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of a condensing agent, if appropriate in the        presence of an acid binder and if appropriate in the presence of        a diluent.

Process (p)

Using 3-iodo-1-methyl-1H-pyrazole-4-carbonyl chloride and1-(2-aminophenyl)ethanone as starting materials, the course of theprocess (p) according to the invention can be illustrated by the formulascheme below:

The iodopyrazolylcarboxylic acid derivatives of the formula (II)required as starting materials for carrying out the process (p)according to the invention have already been described further above, inconnection with the process (a) according to the invention.

Formula (XXII) provides a general definition of the ketoanilinesfurthermore required as starting materials for carrying out the process(p) according to the invention. In this formula (XXII), R¹, R², R³, R⁴,R⁵ and A⁹ preferably, particularly preferably and very particularlypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formulae (I) and(XI) according to the invention as being preferred, particularlypreferred and very particularly preferred, respectively, for theseradicals.

The ketoanilines of the formula (XXII) are known (cf. J. Am. Chem. Soc.1978, 100, 4842-4857 or U.S. Pat. No. 4,032,573), and/or they can beobtained by known methods. If R⁵ does not represent hydrogen, theradical R⁵ can be introduced at the stage of the compounds of theformula (XXII) using customary derivatization methods. It is alsopossible to prepare initially compounds of the formula (VIII) in whichR⁵ represents hydrogen and then to derivatize the products obtainedusing customary methods (cf. the process (i) according to theinvention).

The formula (XII) provides a general definition of the phosphoruscompounds furthermore required as starting materials for carrying outthe process (h) according to the invention.

-   A¹⁰ preferably represents C₂-C₁₀-alkyl which is optionally mono- to    tetrasubstituted by identical or different substituents from the    group consisting of chlorine, fluorine, bromine and    C₃-C₆-cycloalkyl, where the cycloalkyl moiety for its part may    optionally be substituted by halogen and/or C₁-C₄-alkyl.-   A¹⁰ particularly preferably represents in each case straight-chain    or branched ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl,    each of which may be attached in any position and each of which is    optionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of fluorine, cyclopropyl,    difluorocyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.-   Px preferably represents a grouping —P⁺(C₆H₅)₃Cl⁻, —P⁺(C₆H₅)₃Br⁻,    —P⁺(C₆H₅)₃I⁻, —P(═O)(OCH₃)₃ or —P(═O)(OC₂H₅)₃.

The phosphorus compounds of the formula (XII) are known and/or can beprepared by known processes (cf. Justus Liebigs Ann. Chem. 1953, 580,44-57 or Pure Appl. Chem. 1964, 9, 307-335).

Process (i)

UsingN-(4′-chloro-3′-fluoro-1,1′-biphenyl-2-yl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamideand acetyl chloride as starting materials, the course of the process (i)according to the invention can be illustrated by the formula schemebelow:

The formula (Ib) provides a general definition of theiodopyrazolylcarboxanilides required as starting materials for carryingout the process (i) according to the invention. In this formula (Ib),R¹, R², R³, R⁴, R⁶ and Z preferably, particularly preferably and veryparticularly preferably have those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred and very particularly preferred, respectively, for theseradicals.

The compounds of the formula (Ib) are compounds according to theinvention and can be prepared according to processes (a) to (h).

The formula (XIII) provides a general definition of the halidesfurthermore required as starting materials for carrying out the process(i) according to the invention. In this formula (XIII), R⁵⁻¹ preferably,particularly preferably and very particularly preferably has thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (Ig) as being preferred,particularly preferred and very particularly preferred, respectively,for these radicals. X⁶ represents chlorine, bromine or iodine.

Halides of the formula (XIII) are known.

Reaction Conditions

Suitable diluents for carrying out the processes (a), (m), (n), (O) and(p) according to the invention are all inert organic solvents. Thesepreferably include aliphatic, alicyclic or aromatic hydrocarbons, suchas, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; halogenatedhydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,dichloromethane, chloroform, carbon tetrachloride, dichloroethane ortrichloroethane; ethers, such as diethyl ether, diisopropyl ether,methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such asacetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles,such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; mixtures thereof with water or purewater.

The processes (a), (m), (n), (O) and (p) according to the invention are,if appropriate, carried out in the presence of a suitable acid acceptor.Suitable acid acceptors are all customary inorganic or organic bases.These preferably include alkaline earth metal or alkali metal hydrides,hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates,such as, for example, sodium hydride, sodium amide, lithiumdiisopropylamide, sodium methoxide, sodium ethoxide, potassiumtert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate,sodium carbonate, potassium carbonate, potassium bicarbonate, sodiumbicarbonate or ammonium carbonate, and also tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The processes (a), (m), (n), (O) and (p) according to the invention are,if appropriate, carried out in the presence of a suitable condensingagent. Suitable condensing agents are all condensing agents which can becustomarily used for such amidation reactions. Examples which may bementioned are acid halide formers, such as phosgene, phosphorustribromide, phosphorus trichloride, phosphorus pentachloride, phosphorusoxychloride or thionyl chloride; anhydride formers, such as ethylchloroformate, methyl chloroformate, isopropyl chloroformate, isobutylchloroformate or methanesulfonyl chloride; carbodiimides, such asN,N′-dicyclohexylcarbodiimide (DCC), or other customary condensingagents, such as phosphorus pentoxide, polyphosphoric acid,N,N′-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline(EEDQ), triphenylphosphine/carbon tetrachloride orbromotripyrrolidinophosphonium hexafluorophosphate. The processes (a),(m), (n), (O) and (p) according to the invention are, if appropriate,carried out in the presence of a catalyst. Examples which may bementioned are 4-dimethylaminopyridine, 1-hydroxybenzotriazole anddimethylformamide

When carrying out the processes (a), (m), (n), (O) and (p) according tothe invention, the reaction temperatures can be varied within arelatively wide range. In general, the processes are carried out attemperatures of from 0° C. to 150° C., preferably at temperatures offrom 0° C. to 80° C.

For carrying out the process (a) according to the invention forpreparing the compounds of the formula (I), in general from 0.8 to 15mol, preferably from 0.8 to 8 mol, of aniline derivative of the formula(III) are employed per mole of the iodopyrazolylcarboxylic acidderivative of the formula

For carrying out the process (j) according to the invention forpreparing the compounds of the formula (IV), in general from 0.8 to 15mol, preferably from 0.8 to 8 mol, of haloanilines of the formula (XIII)are employed per mole of the iodopyrazolylcarboxylic acid derivative ofthe formula (II).

For carrying out the process (k) according to the invention forpreparing the compounds of the formula (VI), in general from 0.8 to 15mol, preferably from 0.8 to 8 mol, of anilineboronic acid derivative ofthe formula (XIV) are employed per mole of the iodropyrazolylcarboxylicacid derivative of the formula (II).

For carrying out the process (1) according to the invention forpreparing the compounds of the formula (VIII), in general from 0.8 to 15mol, preferably from 0.8 to 8 mol, of hydroxyalkylaniline derivative ofthe formula (XV) are employed per mole of the iodopyrazolylcarboxylicacid derivative of the formula (II).

For carrying out the process (m) according to the invention forpreparing the compounds of the formula (IX), in general from 0.8 to 15mol, preferably from 0.8 to 8 mol, of ketoaniline of the formula (XVI)are employed per mole of the iodopyrazolylcarboxylic acid derivative ofthe formula (II).

Suitable diluents for carrying out the processes (b), (c) and (d)according to the invention are all inert organic solvents. Thesepreferably include aliphatic, alicyclic or aromatic hydrocarbons, suchas, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; ethers, such asdiethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethaneor anisole; nitriles, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulfoxides, such as dimethyl sulfoxide; sulfones, such assulfolane; alcohols, such as methanol, ethanol, n- or i-propanol, n-,i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol,methoxyethanol, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, mixtures thereof with water or pure water.

When carrying out the processes (b), (c) and (d) according to theinvention, the reaction temperatures can be varied within a relativelywide range. In general, the processes are carried out at temperatures offrom 0° C. to 180° C., preferably at temperatures of from 20° C. to 150°C.

The processes (b), (c) and (d) according to the invention are, ifappropriate, carried out in the presence of a suitable acid acceptor.Suitable acid acceptors are all customary inorganic or organic bases.These preferably include alkaline earth metal or alkali metal hydrides,hydroxides, amides, alkoxides, acetates, fluorides, phosphates,carbonates or bicarbonates, such as, for example, sodium hydride, sodiumamide, lithium diisopropylamide, sodium methoxide, sodium ethoxide,potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodiumacetate, sodium phosphate, potassium phosphate, potassium fluoride,cesium fluoride, sodium carbonate, potassium carbonate, potassiumbicarbonate, sodium bicarbonate or cesium carbonate, and also tertiaryamines, such as trimethylamine, triethylamine, tributylamine,N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine,N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU).

The processes (b), (c) and (d) according to the invention are carriedout in the presence of a catalyst, such as, for example, a palladiumsalt or complex. Suitable catalysts are, preferably, palladium chloride,palladium acetate, tetrakis(triphenylphosphine)palladium,bis(triphenyl-phosphine)palladiumdichloride or1,1′-bis(diphenylphosphino)ferrocenepalladium(II) chloride.

It is also possible to generate a palladium complex in the reactionmixture by separately adding a palladium salt and a complex ligand, suchas, for example, triethylphosphine, tri-tert-butylphosphine,tricyclohexylphosphine, 2-(dicyclohexylphosphine)biphenyl,2-(di-tert-butylphosphine)biphenyl,2-(dicyclohexylphosphine)-2′-(N,N-dimethylamino)biphenyl,triphenylphosphine, tris(o-tolyl)phosphine, sodium3-(diphenylphosphino)benzenesulfonate, tris-2-(methoxyphenyl)phosphine,2,2′-bis(diphenylphosphine)-1,1′-binaphthyl,1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)ethane,1,4-bis(dicyclohexylphosphine)butane,1,2-bis(dicyclohexylphosphine)ethane,2-(dicyclohexylphosphine)-2′-(N,N-dimethylamino)biphenyl,bis(diphenylphosphino)ferrocene or tris(2,4-tert-butylphenyl)phosphiteto the reaction.

To carry out the process (b) according to the invention for preparingthe compounds of the formula (I), in general from 1 to 15 mol,preferably from 2 to 8 mol, of the boronic acid derivative of theformula (V) are employed per mole of the haloiodopyrazolylcarboxanilideof the formula (IV).

To carry out the process (c) according to the invention for preparingthe compounds of the formula (I), in general from 0.8 to 15 mol,preferably from 0.8 to 8 mol, of the phenyl derivative of the formula(VII) are employed per mole of the iodopyrazolylcarboxamideboronic acidderivative of the formula (VI).

To carry out the process (d) according to the invention for preparingthe compounds of the formula (I), in general from 0.8 to 15 mol,preferably from 0.8 to 8 mol, of the phenyl derivative of the formula(VII) and from 0.8 to 15 mol, preferably from 0.8 to 8 mol, of4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane are employedper mole of the haloiodopyrazolylcarboxanilide of the formula (IV).

Suitable diluents for carrying out the process (e) according to theinvention are all inert organic solvents. These preferably includealiphatic or alicyclic hydrocarbons, such as, for example, petroleumether, hexane, heptane, cyclohexane, methylcyclohexane or decalin;ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or1,2-diethoxyethane; alcohols, such as methanol, ethanol, n- orisopropanol, n-, iso-, sec- or tert-butanol, ethanediol,propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, mixtures thereofwith water or pure water.

The (e) process according to the invention is carried out in thepresence of a catalyst. Suitable catalysts are all those commonlyemployed for hydrogenations. Examples which may be mentioned are: Raneynickel, palladium and platinum, if appropriate on a support, such as,for example, activated carbon.

Instead of in the presence of hydrogen in combination with a catalyst,the hydrogenation in the process (e) according to the invention can alsobe carried out in the presence of triethylsilane.

When carrying out the process (e) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures of from 0° C. to150° C., preferably at temperatures of from 20° C. to 100° C.

The process (e) according to the invention is carried out under ahydrogen pressure between 0.5 and 200 bar, preferably between 2 and 50bar, particularly preferably between 3 and 10 bar.

Suitable diluents for carrying out the process (f) according to theinvention are all inert organic solvents. These preferably includealiphatic, alicyclic or aromatic hydrocarbons, such as, for example,petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as,for example, chlorobenzene, dichlorobenzene, dichloromethane,chloroform, carbon tetrachloride, dichloroethane or trichloroethane;ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; ketones, such as acetone, butanone,methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile,propionitrile, n- or i-butyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate; sulfoxides, such as dimethyl sulfoxide;sulfones, such as sulfolane; alcohols, such as methanol, ethanol, n- ori-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol,ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, mixtures thereof with water or purewater.

The process (f) according to the invention is, if appropriate, carriedout in the presence of an acid. Suitable acids are all inorganic andorganic protic and Lewis acids, and also all polymeric acids. Theseinclude, for example, hydrogen chloride, sulfuric acid, phosphoric acid,formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid,trifluoromethanesulfonic acid, toluenesulfonic acid, boron trifluoride(also as etherate), boron tribromide, aluminum trichloride, titaniumtetrachloride, tetrabutyl orthotitanate, zinc chloride, iron(III)chloride, antimony pentachloride, acidic ion exchangers, acidic aluminasand acidic silica gel.

When carrying out the process (f) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from 0° C. to150° C., preferably at temperatures of from 0° C. to 100° C.

The processes (f) and (e) according to the invention can also be carriedout in a tandem reaction (“one-pot reaction”). To this end, a compoundof the formula (VIII) is reacted, if appropriate in the presence of adiluent (suitable solvents as for process (f)), if appropriate in thepresence of an acid (suitable acids as for process (f)) and in thepresence of triethylsilane.

Suitable diluents for carrying out the process (g) according to theinvention are all inert organic solvents. These preferably includenitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, or amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide.

The process (g) according to the invention is, if appropriate, carriedout in the presence of a suitable acid acceptor. Suitable acid acceptorsare all customary inorganic or organic bases. These preferably includealkaline earth metal or alkali metal hydrides, hydroxides, amides,alkoxides, acetates, carbonates or bicarbonates, such as, for example,sodium hydride, sodium amide, sodium methoxide, sodium ethoxide,potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammoniumhydroxide, sodium acetate, potassium acetate, calcium acetate, ammoniumacetate, sodium carbonate, potassium carbonate, potassium bicarbonate,sodium bicarbonate or ammonium carbonate, and also tertiary amines, suchas trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The process (g) according to the invention is carried out in thepresence of one or more catalysts.

Suitable catalysts are in particular palladium salts or complexes. Theseare preferably palladium chloride, palladium acetate,tetrakis(triphenylphosphine)palladium orbis-(triphenylphosphine)palladium dichloride. It is also possible togenerate a palladium complex in the reaction mixture by adding apalladium salt and a complex ligand separately to the reaction.

Preferred ligands are organophosphorus compounds. Examples which may bementioned are: triphenylphosphine, tri-o-tolylphosphine,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,dicyclohexylphosphinebiphenyl, 1,4-bis(diphenylphosphino)butane,bisdiphenylphosphinoferrocene, di(tert-butylphosphino)biphenyl,di(cyclohexylphosphino)biphenyl,2-dicyclohexylphosphino-2′-N,N-dimethylaminobiphenyl,tricyclohexylphosphine, tri-tert-butylphosphine. However, ligands mayalso be dispensed with.

Furthermore, the process (g) according to the invention is, ifappropriate, carried out in the presence of a further metal salt, suchas a copper salt, for example copper(I) iodide.

When carrying out the process (g) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from 20° C. to180° C., preferably at temperatures of from 50° C. to 150° C.

For carrying out the process (g) according to the invention forpreparing the compounds of the formula (I), in general from 1 to 5 mol,preferably from 1 to 2 mol, of the alkyne of the formula (IX) or thealkene of the formula (X) are employed per mole of thehaloiodopyrazolylcarboxanilide of the formula (IV).

Suitable diluents for carrying out the process (h) according to theinvention are all inert organic solvents. These preferably includealiphatic, alicyclic or aromatic hydrocarbons, such as, for example,petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as,for example, chlorobenzene, dichlorobenzene, dichloromethane,chloroform, carbon tetrachloride, dichloroethane or trichloroethane;ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; nitriles, such as acetonitrile,propionitrile, n- or i-butyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate; sulfoxides, such as dimethylsulfoxide;sulfones, such as sulfolane; alcohols, such as methanol, ethanol, n- ori-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol,ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether.

The process (h) according to the invention is, if appropriate, carriedout in the presence of a suitable acid acceptor. Suitable acid acceptorsare all customary strong bases. These preferably include alkaline earthmetal or alkali metal hydrides, hydroxides, amides, alkoxides or alkalimetal hydrocarbon compounds, such as, for example, sodium hydride,sodium hydroxide, potassium hydroxide, sodium amide, lithiumdiisopropylamide, sodium methoxide, sodium ethoxide, potassiumtert-butoxide, methyllithium, phenyllithium or butyllithium.

When carrying out the process (h) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from −80° C. to150° C., preferably at temperatures of from −30° C. to 80° C.

To carry out the process (h) according to the invention for preparingthe compounds of the formula (I), in general from 1 to 5 mol, preferablyfrom 1 to 2 mol, of the phosphorus compound of the formula (XII) areemployed per mole of the ketone of the formula (XI).

Suitable diluents for carrying out the process (i) according to theinvention are all inert organic solvents. These preferably includealiphatic, alicyclic or aromatic hydrocarbons, such as, for example,petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as,for example, chlorobenzene, dichlorobenzene, dichloromethane,chloroform, carbon tetrachloride, dichloroethane or trichloroethane;ethers, such as diethyl ether, diisopropyl ether, methyl tert-butylether, methyl tert-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; or amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide.

The process (i) according to the invention is carried out in thepresence of a base. Suitable bases are all customary inorganic ororganic bases. These preferably include alkaline earth metal or alkalimetal hydrides, hydroxides, amides, alkoxides, acetates, carbonates orbicarbonates, such as, for example, sodium hydride, sodium amide, sodiummethoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide,potassium hydroxide, ammonium hydroxide, sodium acetate, potassiumacetate, calcium acetate, ammonium acetate, sodium carbonate, potassiumcarbonate, potassium bicarbonate, sodium bicarbonate or cesiumcarbonate, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process (i) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from 0° C. to150° C., preferably at temperatures of from 20° C. to 110° C.

To carry out the process (i) according to the invention for preparingthe compounds of the formula (I), in general from 0.2 to 5 mol,preferably from 0.5 to 2 mol, of the halide of the formula (XIII) areemployed per mole of the iodopyrazolylcarboxanilide of the formula (Ib).

All processes according to the invention are generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure—in general between 0.1 bar and 10 bar.

The compounds according to the invention have potent microbicidalactivity and can be employed for controlling undesirable microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

Fungicides can be employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes. Bactericides can beemployed in crop protection for controlling Pseudomonadaceae,Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae andStreptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above may be mentioned as examples, but not byway of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The active compounds according to the invention also have very goodfortifying action in plants. Accordingly, they can be used formobilizing the defenses of the plant against attack by undesirablemicroorganisms.

In the present context, plant-fortifying (resistance-inducing)substances are to be understood as meaning those substances which arecapable of stimulating the defense system of plants such that, when thetreated plants are subsequently inoculated with undesirablemicroorganisms, they show substantial resistance to thesemicroorganisms.

In the present case, undesirable microorganisms are to be understood asmeaning phytopathogenic fungi, bacteria and viruses. Accordingly, thesubstances according to the invention can be used to protect plants fora certain period after the treatment against attack by the pathogensmentioned. The period for which protection is provided generally extendsover 1 to 10 days, preferably 1 to 7 days, after the treatment of theplants with the active compounds.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

The active compounds according to the invention can be used withparticularly good results for controlling cereal diseases, such as, forexample, against Puccinia species, diseases in viticulture and in thecultivation of fruit and vegetables, such as, for example, againstBotrytis, Venturia or Alternaria species.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

At certain concentrations and application rates, the active compoundsaccording to the invention can also if appropriate be used asherbicides, for influencing plant growth and for controlling animalpests. If appropriate, they can also be used as intermediates andprecursors for the synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodas meaning all parts and organs of plants above and below the ground,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and plant partswith the active compounds is carried out directly or by allowing thecompounds to act on the surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on, and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

In the protection of materials, the substances according to theinvention can be employed for protecting industrial materials againstinfection with, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaningnonliving materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and heat-transfer liquids, particularlypreferably wood.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular molds, wood-discoloring andwood-destroying fungi (Basidiomycetes), and against slime organisms andalgae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. If the extender used is water, it is also possible to employ,for example, organic solvents as auxiliary solvents. Essentially,suitable liquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide or dimethyl sulfoxide, or else water. Liquefiedgaseous extenders or carriers are to be understood as meaning liquidswhich are gaseous at standard temperature and under atmosphericpressure, for example aerosol propellants such as halogenatedhydrocarbons, or else butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as finely dividedsilica, alumina and silicates. Suitable solid carriers for granules are:for example crushed and fractionated natural rocks such as calcite,marble, pumice, sepiolite and dolomite, or else synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, corn cobs and tobacco stalks. Suitableemulsifiers and/or foam formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulfonates, alkyl sulfates, arylsulfonates, or else proteinhydrolyzates. Suitable dispersants are: for example lignosulfite wasteliquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations, also in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, to broaden, forexample, the activity spectrum or to prevent development of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

Examples of suitable mixing components are the following compounds:

Fungicides:

2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-S-methyl;aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim;anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl;benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos;binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole;bupirimate; buthiobate; butylamine; calcium polysulfide; capsimycin;captafol; captan; carbendazim; carboxin; carpropamid; carvone;chinomethionat; chlobenthiazone; chlorfenazole; chloroneb;chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid;cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb;dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine;dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol;dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap;diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon;edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram;fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin;fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover;flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol;flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al;fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazole;imazalil; imibenconazole; iminoctadine triacetate; iminoctadinetris(albesil); iodocarb; ipconazole; iprobenfos; iprodione;iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin;kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil;metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam;metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil;myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron;nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole;oxycarboxin; oxyfenthiin; paclobutrazole; pefurazoate; penconazole;pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins;polyoxorim; probenazole; prochloraz; procymidone; propamocarb;propanosine-sodium; propiconazole; propineb; proquinazid;prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil;pyroquilon; pyroxyfur; pyrrolenitrine; quinconazole; quinoxyfen;quintozene; simeconazole; spiroxamine; sulfur; tebuconazole;tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole;thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid;tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil;triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin;triflumizole; triforine; triticonazole; uniconazole; validamycin A;vinclozolin; zineb; ziram; zoxamide;(2S)—N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide;1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine;2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide;3,4,5-trichloro-2,6-pyridinedicarbonitrile; actinovate;cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol; methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate;monopotassium carbonate;N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide;N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decane-3-amine; sodiumtetrathiocarbonate; and copper salts and preparations, such as Bordeauxmixture; copper hydroxide; copper naphthenate; copper oxychloride;copper sulfate; cufraneb; cuprous oxide; mancopper; oxine-copper.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulfate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole,acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb,aldoxycarb, allethrin, allethrin 1R-isomers, alpha-cypermethrin(alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541,azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl,azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis,Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillusthuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821,baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb,benfuracarb, bensultap, benzoximate, beta-cyfluthrin,beta-cyper-methrin, bifenazate, bifenthrin, binapacryl, bioallethrin,bioallethrin-5-cyclopentyl-isomer, bioethanomethrin, biopermethrin,bioresmethrin, bistrifluoron, BPMC, brofenprox, bromophos-ethyl,bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505, bufencarb,buprofezin, butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion,carbosulfan, cartap, CGA-50439, chinomethionat, chlordane,chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr,chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate,chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl),chlovapor-thrin, chromafenozide, cis-cypermethrin, cis-resmethrin,cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin,clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene,cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyphenothrin (1R-trans-isomer), cyromazine, DDT,deltamethrin, demeton-S-methyl, demeton-S-methylsulfone, diafenthiuron,dialifos, diazinon, dichlofenthion, dichlorvos, dicofol, dicrotophos,dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobuton,dinocap, dinotefuran, diofenolan, disulfoton, docusat-sodium, dofenapyn,DOWCO-439, eflusilanate, emamectin, emamectin-benzoate, empenthrin(1R-isomer), endosulfan, Entomopthora spp., EPN, esfenvalerate,ethiofencarb, ethiprole, ethion, ethoprophos, etofenprox, etoxazole,etrimfos, famphur, fenamiphos, fenazaquin, fenbutatin oxide,fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxacrim,fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate,fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil, flonicamid,fluacrypyrim, fluazuron, flubenzimine, flubrocythrinate, flucycloxuron,flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin,flupyrazofos, flutenzin (flufenzine), fluvalinate, fonofos, formetanate,formothion, fosmethilan, fosthiazate, fubfenprox (fluproxyfen),furathiocarb, gamma-HCH, gossyplure, grandlure, granulosis viruses,halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron,hexythiazox, hydramethylnone, hydroprene, IKA-2002, imidacloprid,imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos,isoprocarb, isoxathion, ivermectin, japonilure, kadethrin, nuclearpolyhedrosis viruses, kinoprene, lambda-cyhalothrin, lindane, lufenuron,malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium,methacrifos, methamidophos, Metharhizium anisopliae, Metharhiziumflavoviride, methidathion, methiocarb, methomyl, methoprene,methoxychlor, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin,MTI-800, naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide,nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NM-9768,novaluron, noviflumuron, OK-5101, OK-5201, OK-9601, OK-9602, OK-9701,OK-9802, omethoate, oxamyl, oxydemeton-methyl, Paecilomycesfumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-,trans-), petroleum, PH-6045, phenothrin (1R-trans isomer), phenthoate,phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim,piperonyl butoxide, pirimicarb, pirimiphos-methyl, pirimiphos-ethyl,prallethrin, profenofos, promecarb, propaphos, propargite, propetamphos,propoxur, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos,pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion,pyridathion, pyrimidifen, pyriproxyfen, quinalphos, resmethrin, RH-5849,ribavirin, RU-12457, RU-15525, S-421, S-1833, salithion, sebufos,SI-0009, silafluofen, spinosad, spirodiclofen, spiromesifen,sulfluramid, sulfotep, sulprofos, SZI-121, tau-fluvalinate,tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin,temephos, temivinphos, terbam, terbufos, tetrachlorvinphos, tetradifon,tetramethrin, tetramethrin (1R-isomer), tetrasul, theta-cypermethrin,thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogenoxalate, thiodicarb, thiofanox, thiometon, thiosultap-sodium,thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin,triarathene, triazamate, triazophos, triazuron, trichlophenidine,trichlorfon, triflumuron, trimethacarb, vamidothion, vaniliprole,verbutin, Verticillium lecanii, WL-108477, WL-40027, yl-5201, yl-5301,yl-5302, XMC, xylylcarb, ZA-3274, zeta-cypermethrin, zolaprofos,ZXI-8901, the compound 3-methylphenyl propylcarbamate (tsumacide Z), thecompound3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-carbonitrile(CAS-Reg. No. 185982-80-3) and the corresponding 3-endo-isomer (CAS-Reg.No. 185984-60-5) (cf. WO-96/37494, WO-98/25923), and also preparationswhich comprise insecticidally active plant extracts, nematodes, fungi orviruses.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, safeners or semiochemicals, is alsopossible.

In addition, the compounds of the formula (I) according to the inventionalso have very good antimycotic activity. They have a very broadantimycotic activity spectrum in particular against dermatophytes andyeasts, molds and diphasic fungi (for example against Candida species,such as Candida albicans, Candida glabrata), and Epidermophytonfloccosum, Aspergillus species, such as Aspergillus niger andAspergillus fumigatus, Trichophyton species, such as Trichophytonmentagrophytes, Microsporon species such as Microsporon canis andaudouinii. The list of these fungi by no means limits the mycoticspectrum covered, but is only for illustration.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading, etc. It is furthermore possible to apply the activecompounds by the ultra-low-volume method, or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of the plants.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. For the treatment of partsof plants, the active compound application rates are generally between0.1 and 10 000 g/ha, preferably between 10 and 1000 g/ha. For seeddressing, the active compound application rates are generally between0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 gper kilogram of seed. For the treatment of the soil, the active compoundapplication rates are generally between 0.1 and 10 000 g/ha, preferablybetween 1 and 5000 g/ha.

As already mentioned above, it is possible to treat all plants or theirparts in accordance with the invention. In a preferred embodiment, wildplant species or plant varieties and plant cultivars which have beenobtained by traditional biological breeding methods, such ashybridization or protoplast fusion, and the parts of these varieties andcultivars are treated. In a further preferred embodiment, transgenicplants and plant cultivars which have been obtained by recombinantmethods, if appropriate in combination with conventional methods(genetically modified organisms), and their parts are treated. The term“parts” or “parts of plants” or “plant parts” has been explained above.

Plants which are treated particularly preferably in accordance with theinvention are those of the plant cultivars which are in each casecommercially available or in use. Plant cultivars are understood asmeaning plants with new traits which have been bred either byconventional breeding, by mutagenesis or by recombinant DNA techniques.They may take the form of cultivars, breeds, biotypes and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, nutrition), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widened activity spectrum and/or an increase in the activity ofthe substances and compositions which can be used in accordance with theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to salinity in the wateror soil, increased flowering performance, facilitated harvesting,accelerated maturation, higher yields, higher quality and/or betternutritional value of the harvested products, better storagecharacteristics and/or processability of the harvested products arepossible which exceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (those obtained byrecombinant methods) to be treated in accordance with the inventioninclude all those plants which, owing to the process of recombinantmodification, were given genetic material which confers particular,advantageous, valuable traits to these plants. Examples of suchproperties are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to salinity in the wateror soil, increased flowering performance, facilitated harvesting,accelerated maturation, higher yields, higher quality and/or highernutritional value of the harvested products, better storagecharacteristics and/or better processability of the harvested products.Further examples of such traits, examples which are mentionedespecially, are better defense of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses and an increased tolerance of the plants tocertain herbicidal active compounds. Examples of transgenic plants whichmay be mentioned are the important crop plants, such as cereals (wheat,rice), corn, soybeans, potatoes, cotton, tobacco, oilseed rape and fruitplants (with the fruits apples, pears, citrus fruits and grapes), withparticular emphasis on corn, soybeans, potatoes, cotton, tobacco, andoilseed rape. Traits which are especially emphasized are the increaseddefense of the plants against insects, arachnids, nematodes, and slugsand snails owing to toxins being formed in the plants, in particulartoxins which are generated in the plants by the genetic material ofBacillus thuringiensis (for example by the genes CryIA(a), CryIA(b),CryIA(c), CryIIA, CryIIIA, CryMB2, Cry9c Cry2Ab, Cry3Bb and CryIF andtheir combinations; hereinbelow “Bt plants”). Other traits which areparticularly emphasized are the increased defense of plants againstfungi, bacteria and viruses by the systemic acquired resistance (SAR),systemin, phytoalexins, elicitors and resistance genes andcorrespondingly expressed proteins and toxins. Other traits which areespecially emphasized are the increased tolerance of the plants tocertain herbicidal active compounds, for example imidazolinones,sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene).The genes which confer the desired traits in each case may also bepresent in the transgenic plants in combination with one another.Examples of “Bt plants” which may be mentioned are corn cultivars,cotton cultivars, soybean cultivars and potato cultivars which arecommercially available under the trade names YIELD GARD® (for examplecorn, cotton, soybean), KnockOut® (for example corn), StarLink® (forexample corn), Bollgard® (cotton), Nucoton® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare corn cultivars, cotton cultivars and soybean cultivars which arecommercially available under the trade names Roundup Ready® (toleranceto glyphosate, for example corn, cotton, soybean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulfonylureas, forexample corn). Herbicide-resistant plants (plants bred in a conventionalmanner for herbicide tolerance) which may be mentioned include also thevarieties commercially available under the name Clearfield® (for examplecorn). Naturally, these statements also apply to plant cultivars havingthese genetic traits or genetic traits still to be developed, whichplant cultivars will be developed and/or marketed in the future.

The plants listed can be treated particularly advantageously accordingto the invention with the compounds of the general formula (I) or theactive compound mixtures according to the invention. The preferredranges stated above for the active compounds and mixtures also apply tothe treatment of these plants. Particular emphasis may be given to thetreatment of plants with the compounds or mixtures specificallymentioned in the present text.

The preparation and the use of the active compounds according to theinvention is illustrated in the examples below.

PREPARATION EXAMPLES Example 1

At room temperature, 273 mg (1.0 mmol) of3-iodo-1-methyl-1H-pyrazole-4-carboxylic acid, 213 mg (0.83 mmol) of3′,4′-dichloro-5-fluorobiphenyl-2-amine, 0.3 ml (1.67 mmol) ofN,N-diisopropyl-ethylamine and 583 mg (1.25 mmol) ofbromotripyrrolidinophosphonium hexafluorophosphate were stirred in 5 mlof methylene chloride for 3 days. The mixture was washed with saturatedsodium bicarbonate solution and then with water. Removal andconcentration of the organic phase gave 910 mg of crude product.Purification by column chromatography on silica gel 60 using methylenechloride/diethyl ether 5:1 gave 230 mg (53.5% of theory) ofN-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-iodo-1-methyl-1H-pyrazole-4-carboxamide(compound No. 6 from table 1) of log P (pH 2.3)=3.42.

The compounds of the formula (I) listed in table 1 below were alsoobtained analogously to example 1 and in accordance with the statementsin the general description of the preparation processes (a) to (i)according to the invention:

TABLE 1 (1)

No. Z R⁴ R⁶ R⁵ R³ R² R¹ logP 1 1,3,3-trimethylbutyl H CH₃ H H H H 3.64 23,4-dichlorophenyl H CH₃ H H H H 3.38 3 4-chloro-3-fluorophenyl H CH₃ HH H H 3.09 4 1,3-dimethylbutyl H CH₃ H H H H 3.36 53-fluoro-4-propoxyiminomethyl- H CH₃ H H H H 4.00 phenyl 63,4-dichlorophenyl H CH₃ H F H H 3.42 7 3-fluoro-4-methylphenyl H CH₃ HH H H 3.18 8 3-chloro-4-fluorophenyl H CH₃ H H H H 3.09 9 4-bromophenylH CH₃ H H H H 3.20 10 4-trifluoromethylphenyl H CH₃ H H H H 3.24 113-fluoro-4-trifluoromethylphenyl H CH₃ H H H H 3.23 121,3-dimethyl-1-butenyl H CH₃ H H H H 3.62 13 1-hydroxy-1,3-dimethyl-3- HCH₃ H H H H 2.54 butenyl 14 4-chlorophenyl H CH₃ H H H H 3.08 152-cyclopropyl-1-methylethyl H CH₃ H H H H 3.08 16 4-iodophenyl H CH₃ H HH H 3.36 17 3-chloro-2-fluorophenyl H CH₃ H H H H 2.99 183,3-dimethylbutyl H CH₃ H H H H 3.34 19 —CH(CH₃)—CH₂—C(CH₃)₂— CH₃ H H HH 3.27 20 1,3-dimethylbutyl H CH₃ H F H H 3.39 21 1,3-dimethylbutyl HCH₃ COCH₃ H H H 3.68 22 3,3-dimethylbutynyl H CH₃ H H H H 3.79 23

H CH₃ H H H H 3.70 24 3-methylbutyl H CH₃ H H H H 3.15 251-(1-methylethyl)ethenyl H CH₃ H H H H 3.28 261-(2,2-dimethylpropyl)ethenyl H CH₃ H H H H 3.82 27 1,2-dimethylpropenylH CH₃ H H H H 3.40 28 2,3-dichlorophenyl H CH₃ H H H H 3.34 294-chloro-3-fluorophenyl H CH₃ H H H F 2.78 30 2-chloro-4-trifluoro- HCH₃ H H H H 3.55 methylphenyl 31 4-bromo-3-chlorophenyl H CH₃ H H H H3.45 32 4-bromo-2-chlorophenyl H CH₃ H H H H 3.56

Preparation of the Starting Materials of the Formula (II) Example (II-1)

Step 1:

13 ml of isoamyl nitrite were initially charged in 80 ml of methyleneiodide. At 100° C., 10.2 g (60.3 mmol) of ethyl3-amino-1-methyl-1H-pyrazole-4-carboxylate (XIV-1) were added dropwise.After 15 min of stirring at this temperature, the mixture wasconcentrated.

This gave 15.2 g (79% of theory) of ethyl3-iodo-1-methyl-1H-pyrazole-4-carboxylate [log P (pH 2.3)=1.74] whichwas used without further work-up.

Step 2:

134 g (0.478 mol) of ethyl 3-iodo-1-methyl-1H-pyrazole-4-carboxylatewere initially charged in 850 ml of ethanol, and a solution of 29.5 g(0.526 mol) of KOH in 340 ml of water was added dropwise. After 2 daysof stirring at room temperature, the mixture was concentrated, theresidue was taken up in water and extracted with ethyl acetate and,after separation, the aqueous phase was adjusted to pH 1 usinghydrochloric acid, resulting in the precipitation of a solid. Filtrationwith suction and 3 hours of drying under reduced pressure at 40° C. gave88 g (70% of theory) of 3-iodo-1-methyl-1H-pyrazole-4-carboxylic acid[log P (pH 2.3)=0.57]. The aqueous phase was extracted with ethylacetate and the organic phase was concentrated, which gave another 5.1 g(2.1% of theory) of product.

Preparation of the Starting Materials of the Formula (XIV) Example(XIV-1)

At room temperature, 100 ml of concentrated hydrochloric acid were addeddropwise over a period of 20 min to a suspension of 220 g (0.855 mol) ofethyl 3-(N′-benzylidene-N-methylhydrazino)-2-cyanoacrylate (XVI-1) in1000 ml of ethanol. The mixture was then heated at the boil for 1 hour.After removal of the solvent, the oily residue was triturated withgentle heating with 200 ml of diethyl ether, resulting in theprecipitation of a solid. Filtration with suction gave 149 g (95% oftheory) of ethyl 3-amino-1-methyl-1H-pyrazole-4-carboxylate [log P (pH2.3)=0.72].

Preparation of the Starting Materials of the Formula (XVI) Example(XVI-1)

258 g (1.92 mol) of N-benzylidene-/V′-methylhydrazine and 325 g (1.92mol) of ethyl ethoxy-methylenecyanoacetate were initially charged in1000 ml of toluene and heated at the boil for 1 hour. After cooling, themixture was filtered off with suction, which gave 447 g (89.5% oftheory) of ethyl 3-(N′-benzylidene-N-methylhydrazino)-2-cyanoacrylate[log P (pH 2.3)=2.31]. The filtrate was allowed to stand for 16 hoursand then again filtered off with suction, which gave another 7.7 g (1.5%of theory) of the desired product.

The given log P values were determined in accordance with EEC directive79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on areversed-phase column (C18). Temperature: 43° C.

Mobile phases for the determination in the acidic range (pH 2.3): 0.1%aqueous phosphoric acid, acetonitrile; linear gradient from 10%acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (having 3 to16 carbon atoms) with known log P values (determination of the log Pvalues by the retention times using linear interpolation between twosuccessive alkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

Use Examples Example A Podosphaera Test (Apple)/Protective

Solvents: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvents andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of the apple mildew pathogen Podosphaera leucotricha.The plants are then placed in a greenhouse at about 23° C. and arelative atmospheric humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE A Podosphaera test (apple)/protective Active compound applicationActive compound according rate Efficacy to the invention in g/ha in %

100 100

100 100

100 99

100 100

100 100

100 100

100 100

100 100

100 100

100 88

100 99

100 100

100 100

100 98

100 100

100 100

Example B Venturia Test (Apple)/Protective

Solvents: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvents andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousconidia suspension of the apple pathogen Venturia inaequalis and thenremain in an incubation cabin at about 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at about 21° C. and arelative atmospheric humidity of about 90%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE B Venturia test (apple)/protective Active compound applicationActive compound according rate Efficacy to the invention in g/ha in %

100 100

100 100

100 99

100 100

100 100

100 100

100 100

100 100

100 97

100 94

100 98

100 100

100 99

100 98

100 100

100 100

Example C Botrytis Test (Bean)/Protective

Solvents: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvents andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, 2 small pieces of agar colonized withBotrytis cinerea are placed onto each leaf. The inoculated plants areplaced in a darkened chamber at about 20° C. and 100% relativeatmospheric humidity.

2 days after the inoculation, the size of the infected areas on theleaves is evaluated. 0% means an efficacy which corresponds to that ofthe control, whereas an efficacy of 100% means that no infection isobserved.

Active compounds, application rates and test results are shown in thetable below.

TABLE C Botrytis test (bean)/protective Active compound applicationActive compound according rate Efficacy to the invention in g/ha in %

500 100

500 100

500 100

100 100

500 100

500 100

500 100

500 100

500 100

500 94

500 100

100 100

100 100

100 98

100 100

100 100

Example D Pyrenophora teres Test (Barley)/Protective

Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Pyrenophora teres. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature of about 20°C. and a relative atmospheric humidity of about 80%.

Evaluation is carried out 8 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE D Pyrenophora test (barley)/protective Active compound applicationActive compound according rate Efficacy to the invention in g/ha in %

500 93

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

Example E Puccinia Test (Wheat)/Protective

Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Puccinia recondita. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature of about 20°C. and a relative atmospheric humidity of 80% to promote the developmentof rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE E Puccinia test (wheat)/protective Active compound applicationActive compound according rate Efficacy to the invention in g/ha in %

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

500 100

Example F Alternaria Test (Tomato)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young tomato plants are sprayed withthe preparation of active compound at the stated application rate. 1 dayafter the treatment, the plants are inoculated with a spore suspensionof Alternaria solani and are then allowed to stand at 100% relativeatmospheric humidity and 20° C. for 24 h. The plants are then allowed tostand at 96% relative atmospheric humidity and a temperature of 20° C.

The evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE F Alternaria test (tomato)/protective Active compound applicationActive compound according rate Efficacy to the invention in g/ha in %

750 100

750 100

750 100

1-10. (canceled)
 11. An iodopyrazolylcarboxylic acid derivative offormula (II)

in which R⁶ represents C₁-C₃-alkyl, C₁-C₂-alkoxy-C₁-C₂-alkyl, orC₁-C₃-haloalkyl having 1 to 7 fluorine, chlorine, and/or bromine atoms,and X¹ represents chlorine or hydroxyl.
 12. A process for preparing aniodopyrazolylcarboxylic acid derivative of formula (II)

in which R⁶ represents C₁-C₃-alkyl, C₁-C₂-alkoxy-C₁-C₂-alkyl, orC₁-C₃-haloalkyl having 1 to 7 fluorine, chlorine, and/or bromine atoms,and X¹ represents chlorine or hydroxyl, comprising (i) in a first stepreacting a 3-aminopyrazole-4-carboxylic ester of formula (XIV)

in which Alk represents C₁-C₄-alkyl, and R⁶ represents C₁-C₃-alkyl,C₁-C₂-alkoxy-C₁-C₂-alkyl, or C₁-C₃-haloalkyl having 1 to 7 fluorine,chlorine, and/or bromine atoms, with an iodinating agent in the presenceof isoamyl nitrite to form a 3-iodo-pyrazole-4-carboxylic ester offormula (XV)

in which Alk and R⁶ are as defined for formula (XIV), and (ii) in asecond step hydrolyzing the 3-iodopyrazole-4-carboxylic ester of formula(XV) to the corresponding acid of formula (II) in which X¹ is hydroxylwith a base in the presence of a diluent, and (iii) optionally in athird step, reacting the resultant acid from the second step with achlorinating agent in the presence of a diluent to give thecorresponding acid chloride of formula (II) in which X¹ is chlorine.